CN111725490A - Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof - Google Patents
Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material, a preparation method thereof and application thereof in electrochemical energy storage. Firstly, a polyvinyl alcohol sol system is utilized to mix soluble niobium sources, organic nitrogen sources and other raw materials at the molecular level in the sol system, the full precipitation reaction is ensured, then high-temperature carbonization treatment is carried out, the carbon coating and nitrogen doping on the surface of niobium pentoxide are further realized, and the particle size of the niobium pentoxide is further regulated and controlled; the obtained niobium pentoxide particles have small particle size and are uniformly distributed. In the electrochemical reaction, the ultrafine niobium pentoxide particles can effectively shorten the mass transfer distance, and the introduced heterogeneous elements and carbon coating can well solve the problems of poor conductivity and volume expansion effect of metal oxides, thereby greatly improving the electrochemical energy storage performance of the composite material. The method is simple, convenient and environment-friendly, has low cost, and has important scientific significance and wide application prospect.
Description
Technical Field
The invention belongs to the field of nano composite materials and electrochemical energy storage, and particularly relates to a nitrogen-doped carbon-coated superfine niobium pentoxide nano composite material and a preparation method thereof.
Background
In recent years, in order to meet the requirement of large-scale energy storage, an ideal secondary battery has excellent electrochemical performance and also has social and economic benefit indexes of abundant resources, low price, cleanness, environmental protection and the like. The metal oxide niobium pentoxide attracts wide attention of scholars at home and abroad as a potential electrochemical energy storage material. Each octahedron of a (001) surface in the crystal structure of the niobium pentoxide can provide 4 storage points, and the edge length of about 0.39nm can provide a special and wide ion channel, so that lithium ions and sodium ions can be stored, and the specific capacity and the energy density of storage are improved. Although metal oxide materials may exhibit large reversible capacity, the capacity loss during cycling is large, i.e., the cycling stability is poor, especially the first time capacity loss is large. Meanwhile, the conductive material has poor conductivity, large volume change in the charge and discharge process and unstable structure.
To solve this problem, the carbon coating method is widely used. The carbon material has abundant energy storage sites and excellent electrical conductivity, and can effectively improve the problems of poor electrical conductivity of niobium pentoxide and inhibit the volume expansion effect of niobium pentoxide in the charge-discharge cycle process. However, the small pitch of carbon layers and the large specific surface area of carbon cause a large amount of electrolyte decomposition during the formation of a solid electrolyte interface film (SEI), resulting in low initial coulombic efficiency. Research shows that nitrogen has strong electronegativity, and nitrogen doping can remarkably increase the distance between carbon layers and accelerate the diffusion kinetics of sodium ions. Although the problems of conductivity and volume effect can be effectively solved by nitrogen doping and carbon coating, the preparation of niobium pentoxide with a proper particle size is also important in order to prevent niobium pentoxide particles from agglomerating in the charging and discharging processes. The traditional method for synthesizing niobium pentoxide mainly comprises a hydrothermal method, a solvothermal method, a direct precipitation method, an electrostatic spinning method and the like, but is influenced by the problems of expensive synthetic raw materials, more complicated operation, inconsistent synthesized particle size, uneven distribution, more serious particle agglomeration and the like, so that the application of the niobium pentoxide in chemical energy storage is greatly limited. Therefore, further exploring a simple and feasible method for preparing the nitrogen-doped carbon-coated niobium pentoxide composite nanomaterial with a proper particle size has important significance for improving the energy storage performance and accelerating the popularization and application of niobium pentoxide.
Disclosure of Invention
Aiming at the technical defects and improvement requirements in the prior art, the invention mainly aims to provide a nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and a preparation method thereof; according to the invention, the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite is synthesized by a sol-gel method and high-temperature calcination, so that on one hand, the raw materials are mixed at a molecular level by the sol-gel method, the reaction is more sufficient, the agglomeration among particles is reduced, the distribution is more uniform, and the formed ultrafine niobium pentoxide nanoparticles can effectively shorten the mass transfer distance; on the other hand, the decomposition of organic matters in the high-temperature sintering process can lead nitrogen to be doped in situ, and the problems of the electrical conductivity and the volume expansion of the niobium pentoxide are fully improved due to the synergistic effect between carbon and nitrogen.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
a nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and a preparation method thereof adopt a method combining sol-gel and high-temperature calcination, and specifically comprise the following steps:
1) adding polyvinyl alcohol into water, and magnetically stirring in a constant-temperature water bath to obtain transparent colloidal liquid;
2) adding a niobate solution into the transparent colloidal liquid obtained in the step 1), adding an organic nitrogen source after uniformly mixing, and carrying out magnetic stirring under the condition of constant-temperature water bath;
3) adding an alkaline precipitator into the mixture obtained in the step 2), adding a cross-linking agent after the precipitation reaction is completed, and fully stirring to obtain a brown yellow colloid;
4) uniformly smearing the brown yellow colloid obtained in the step 3) on a glass plate and storing the glass plate in a drying box overnight for gelation and aging;
5) and (3) carrying out high-temperature calcination pyrolysis on the dried gel obtained in the step 4) in an inert atmosphere to obtain the nitrogen-doped carbon-coated niobium pentoxide nanocomposite.
In the scheme, the concentration of polyvinyl alcohol introduced into water in the step 1) is 0.1-0.25 g/ml.
In the scheme, the water bath temperature in the step 1) is 90-95 ℃, and the magnetic stirring time is 2-4 h.
In the above scheme, the niobium salt in step 2) is at least one of niobium oxalate, niobium pentachloride, niobium fluoride and niobium acetate.
In the scheme, the concentration of the niobate solution in the step 2) is 0.125-0.55 g/ml.
In the scheme, the organic nitrogen source in the step 2) is melamine; the mass ratio of the introduced polyvinyl alcohol to the melamine is 1 (0.1-1).
In the scheme, the temperature of the constant-temperature water bath in the step 2) is 65-75 ℃, and the magnetic stirring time is 1-2 hours.
In the scheme, the alkaline precipitator in the step 3) is at least one of ammonium carbonate, ammonium hydroxide and ammonium bicarbonate, and the mass ratio of the alkaline precipitator to the niobium salt is (1-3): 1.
In the scheme, the cross-linking agent in the step 3) is glutaraldehyde, and the mass ratio of the cross-linking agent to the polyvinyl alcohol is (0.5-0.8): 1.
In the scheme, the drying temperature in the step 4) is 60-80 ℃, and the gel aging time is 12-15 h.
In the scheme, the inert atmosphere in the step 5) is argon atmosphere and the like.
In the scheme, the calcining process in the step 5) comprises the following steps: firstly, heating to 200-250 ℃, and preserving heat for 0.5-1 h; then the temperature is raised to 550-800 ℃, and the temperature is kept for 2-3 h.
In the scheme, the heating rate in the step 5) is 2-5 ℃/min.
The nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite prepared according to the scheme has a very small particle size of about 8-10 nm and regular and clear crystal lattice stripes, wherein the content of nitrogen element is 3.0-6.0 at.%.
The invention combines a sol-gel method and a high-temperature calcination method, uses polyvinyl alcohol to form a sol precursor solution, then mixes the sol precursor solution with niobium oxalate and an organic nitrogen source, carries out precipitation reaction under an alkaline condition, and finally adds a cross-linking agent to carry out gelation, aging and high-temperature calcination to obtain the nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material: the adopted polyvinyl alcohol sol system can promote the niobium oxalate and the organic nitrogen source to fully contact and uniformly mix, and ensure more complete precipitation reaction under alkaline conditions; after the reaction is completed, adding a cross-linking agent glutaraldehyde to solidify the polyvinyl alcohol, so that the generated niobium hydroxide is cured in situ in a polyvinyl alcohol system, and the agglomeration of the niobium hydroxide is avoided; then, a high-temperature calcination process is further combined, niobium hydroxide is decomposed to form niobium pentoxide during high-temperature treatment, a carbon layer formed by decomposition of organic matters can uniformly coat the niobium pentoxide, the particle size of the niobium pentoxide is further controlled, the agglomeration phenomenon of particles is effectively inhibited, and the particles are uniform and good in dispersibility; the method for doping the heterogeneous elements can ensure that the heterogeneous elements are uniformly distributed in pores or layers of carbon, has higher activity and can effectively promote the electrochemical performance of the obtained nano composite material; and the related preparation method is simple, low in cost, green and environment-friendly, and is suitable for popularization and application.
Compared with the prior art, the invention has the beneficial effects that:
1) the nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite provided by the invention has small particles, the average particle size can reach 8nm, the agglomeration phenomenon is light, the particles are uniform, and the dispersibility is good; the components are uniformly distributed, the conductivity is good, the electron migration speed is high, the amount of stored or adsorbed ions or electrons is large, the energy storage performance is excellent, and the electrochemical energy storage material can be widely applied to the field of electrochemical energy storage.
2) According to the invention, a sol-gel mixing mode is adopted to realize full contact and uniform mixing of various substances of heterogeneous elements, namely nitrogen, niobium oxalate, inorganic base and a cross-linking agent in a polyvinyl alcohol sol system, so that the reaction is more sufficient, and the phenomena of particle agglomeration and non-uniform particle size are effectively inhibited during high-temperature carbonization; heterogeneous element nitrogen is uniformly distributed in pores or among layers of carbon, so that the activity is higher, and the electrochemical performance of the obtained nano composite material can be effectively promoted; and the related preparation method is simple, low in cost and environment-friendly.
3) According to the invention, the nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite is prepared by researching and setting the composite proportion, the carbonization conditions and the like, and the reversible specific capacity can still be kept at 270.6mAh/g after 100 times of circulation under the current density of 0.1A/g relative to the undoped coated niobium pentoxide; as a potential negative electrode material of the battery, the electrochemical performance is good.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite prepared in example 1 of the present invention at different magnifications;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) analysis of the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite prepared in example 1 of the present invention.
Fig. 3 is a comparison graph of the sodium storage cycle performance of a sodium ion battery assembled by using the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite material prepared in example 1 of the present invention and the niobium pentoxide-based material prepared in comparative example 1.
FIG. 4 is a comparison graph of the sodium storage cycle performance of a sodium-ion battery assembled by using the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite prepared in example 1 of the present invention and the nanocomposite obtained in comparative example 2, and a comparison group.
Fig. 5 is a diagram showing the sodium storage cycle rate performance of a sodium ion battery assembled by using the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material is prepared by the following steps:
1) weighing 2.0g of polyvinyl alcohol, adding the polyvinyl alcohol into 12mL of deionized water, magnetically stirring for 2 hours under the condition of constant-temperature water bath at 95 ℃, and dissolving and dispersing to obtain transparent colloidal liquid I;
2) weighing 0.5g of niobium oxalate, dissolving in 3mL of ionized water, adding into the transparent colloidal liquid I obtained in the step 1), after uniformly mixing, adding an organic nitrogen source according to the mass ratio of polyvinyl alcohol to melamine of 1:0.1, and magnetically stirring for 2 hours under the condition of a constant-temperature water bath at 70 ℃;
3) adding 1.0g of ammonium hydroxide into the mixture obtained in the step 2), adding 1.5g of glutaraldehyde after the precipitation reaction is completed, and fully stirring to obtain a brown yellow colloid;
4) the brownish yellow colloid obtained in step 3) was spread evenly on a glass plate and stored overnight in a 60 ℃ drying cabinet for gelation and aging to give a dry gel.
5) And placing the obtained dried gel in a tubular furnace in an argon atmosphere, heating to 200 ℃ at the heating rate of 2 ℃/min, preserving heat for 0.5h, heating to 600 ℃ and preserving heat for 2h, and naturally cooling to obtain the nitrogen-doped carbon-coated niobium pentoxide nanocomposite.
Fig. 1 is a Transmission Electron Microscope (TEM) image of the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in the present example under different magnifications, and it can be seen from fig. 1 that the obtained product has a small particle size (about 8-10 nm), a light agglomeration phenomenon, uniform particles, good dispersibility, and regular and clear lattice fringes; the method is not only beneficial to the diffusion of the electrolyte in the composite material, but also can effectively shorten the mass transfer distance and be beneficial to the rapid migration of electrons.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) graph of the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in the present example, which shows that the product mainly contains C, N, O, Nb four elements, wherein the content of nitrogen element is 5.17 at.%.
Example 2
A nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material is prepared by the following steps:
1) weighing 1.5g of polyvinyl alcohol, adding the polyvinyl alcohol into 12mL of deionized water, magnetically stirring for 2 hours under the condition of constant-temperature water bath at 90 ℃, and dissolving and dispersing to obtain transparent colloidal liquid I;
2) weighing 0.5g of niobium oxalate, dissolving in 3mL of ionized water, adding into the transparent colloidal liquid I obtained in the step 1), after uniformly mixing, adding an organic nitrogen source according to the mass ratio of polyvinyl alcohol to melamine of 1:0.2, and magnetically stirring for 2 hours under the condition of a constant-temperature water bath at 70 ℃;
3) adding 1.0g of ammonium bicarbonate into the mixture obtained in the step 2), adding 1.0g of glutaraldehyde after complete precipitation, and fully stirring to obtain a brown yellow colloid;
4) the brownish yellow colloid obtained in step 3) was spread evenly on a glass plate and stored overnight in a 60 ℃ drying cabinet for gelation and aging to give a dry gel.
5) And placing the obtained dry gel in a tubular furnace in an argon atmosphere, heating to 200 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, heating to 800 ℃ and preserving heat for 2h, and naturally cooling to obtain the nitrogen-doped carbon-coated niobium pentoxide nanocomposite.
Through tests, the content of nitrogen element in the nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material obtained in the embodiment is 3.03 at.%.
Example 3
A nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material is prepared by the following steps:
1) weighing 2.5g of polyvinyl alcohol, adding the polyvinyl alcohol into 13mL of deionized water, magnetically stirring for 2 hours under the condition of a constant-temperature water bath at 90 ℃, and dissolving and dispersing to obtain a transparent colloidal liquid I;
2) weighing 1.0g of niobium oxalate, dissolving in 4mL of ionized water, adding into the transparent colloidal liquid I obtained in the step 1), after uniformly mixing, adding an organic nitrogen source according to the mass ratio of polyvinyl alcohol to melamine of 1:0.2, and magnetically stirring for 2 hours under the condition of a constant-temperature water bath at 65 ℃;
3) adding 2.0g of ammonium hydroxide into the mixture obtained in the step 2), adding 1.5g of glutaraldehyde after the precipitate is completely precipitated, and fully stirring to obtain a brown yellow colloid;
4) the brownish yellow colloid obtained in step 3) was spread evenly on a glass plate and stored overnight in a 60 ℃ drying cabinet for gelation and aging to give a dry gel.
5) And placing the obtained dried gel in a tubular furnace in an argon atmosphere, heating to 200 ℃ at the heating rate of 4 ℃/min, preserving heat for 0.5h, heating to 700 ℃ and preserving heat for 3h, and naturally cooling to obtain the nitrogen-doped carbon-coated niobium pentoxide nanocomposite.
Through tests, the content of nitrogen element in the nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite material obtained in the embodiment is 3.88 at.%.
Comparative example 1
The nitrogen-free doped carbon-coated pure niobium pentoxide prepared by a direct precipitation method comprises the following specific preparation steps: weighing 0.5g of niobium oxalate, dissolving in 3mL of ionized water, adding 1mmoL of ammonium hydroxide, and after precipitation is completed, obtaining pure niobium pentoxide powder by the drying and carbonization processes in the steps 4) and 5) of the embodiment 1.
Comparative example 2
This comparative example was prepared substantially identically to the preparation described in example 1, except that: and 3) adding no cross-linking agent glutaraldehyde.
Application example
The nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite obtained in example 1 of the invention and the pure niobium pentoxide powder obtained in comparative example 1 are respectively applied to the preparation of a sodium-ion battery, and the specific assembly method comprises the following steps: the niobium pentoxide-based material obtained in example 1 or comparative example 1 and comparative example 2, conductive carbon and a binder are uniformly mixed in a solvent according to the mass ratio of 8:1:1 and coated on a copper foil, and the mixture is dried, cold-pressed and punched to form an electrode plate, and the electrode plate is assembled into a sodium ion battery.
Fig. 3 is a diagram showing the sodium storage cycle performance of a sodium ion battery assembled by using the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in example 1 and the niobium pentoxide-based material obtained in comparative example 1, and shows that the reversible specific capacity of the nanocomposite obtained in the present invention can be maintained at 270.6mAh/g after 100 cycles at a current density of 0.1A/g, which shows that the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in the present invention also exhibits good cycle stability performance while improving the sodium storage performance.
Fig. 4 is a diagram showing the sodium storage cycle performance of a sodium ion battery assembled by using the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in example 1 and the nanocomposite obtained in comparative example 2, respectively, and shows that the reversible specific capacity of the nanocomposite obtained without adding the crosslinking agent glutaraldehyde is only 170.2mAh/g after 100 cycles at a current density of 0.1A/g.
Fig. 5 is a sodium storage cycle rate performance diagram of a sodium ion battery assembled by the nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite obtained in example 1, and the diagram shows that the nanocomposite obtained by preparation has high reversible specific capacity under high current density and shows good sodium storage performance.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite is characterized by comprising the following steps:
1) adding polyvinyl alcohol into water, and magnetically stirring in a constant-temperature water bath to obtain transparent colloidal liquid;
2) adding a niobate solution into the transparent colloidal liquid obtained in the step 1), uniformly mixing, adding an organic nitrogen source, and carrying out magnetic stirring under the condition of a constant-temperature water bath;
3) adding an alkaline precipitator into the mixture obtained in the step 2), adding a cross-linking agent after the precipitation reaction is completed, and fully stirring to obtain a brown yellow colloid;
4) uniformly coating the brown yellow colloid obtained in the step 3) on a glass plate, and gelling and aging in a drying oven;
5) and (3) carrying out high-temperature calcination pyrolysis on the dried gel obtained in the step 4) in an inert atmosphere to obtain the nitrogen-doped carbon-coated niobium pentoxide nanocomposite.
2. The method according to claim 1, wherein the concentration of polyvinyl alcohol introduced into water in step 1) is 0.1 to 0.25 g/ml.
3. The preparation method of claim 1, wherein the water bath temperature in the step 1) is 90-95 ℃, and the magnetic stirring time is 2-4 h.
4. The method according to claim 1, wherein the niobium salt in step 2) is at least one of niobium oxalate, niobium acetate, niobium chloride, and niobium fluoride; the organic nitrogen source in the step 2) is melamine.
5. The method according to claim 1, wherein the concentration of the niobate solution in the step 2) is 0.125 to 0.55 g/ml; the mass ratio of the introduced polyvinyl alcohol to the organic nitrogen source is 1 (0.1-1).
6. The preparation method according to claim 1, wherein the temperature of the constant-temperature water bath in the step 2) is 65-75 ℃, and the magnetic stirring time is 1-2 hours.
7. The preparation method according to claim 1, wherein the alkaline precipitant in step 3) is at least one of ammonium carbonate, ammonium hydroxide and ammonium bicarbonate, and the mass ratio of the alkaline precipitant to the niobium salt is (1-3): 1.
8. The preparation method of claim 1, wherein the cross-linking agent in the step 3) is glutaraldehyde, and the mass ratio of the cross-linking agent to the polyvinyl alcohol is (0.5-0.8): 1.
9. The preparation method according to claim 1, wherein the calcination process in step 5) is: firstly, heating to 200-250 ℃, and preserving heat for 0.5-1 h; then the temperature is raised to 550-800 ℃, and the temperature is kept for 2-3 h.
10. The nitrogen-doped carbon-coated ultrafine niobium pentoxide nanocomposite material prepared by the preparation method according to any one of claims 1 to 9, which has a particle size of 8 to 10nm and a regular and clear lattice fringe, wherein the nitrogen element content is 3.0 to 6.0 at.%.
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